Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2.
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Outros Autores: | |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFOP |
Texto Completo: | http://www.repositorio.ufop.br/handle/123456789/4489 https://doi.org/10.1016/j.poly.2006.06.020 |
Resumo: | Crystals of the new one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2 (Pc = C32H16N8) were grown directly from phthalonitrile and pure zirconium powder under the oxidation conditions of IBr at 220 _C. [ZrPc2]IBr2 crystallises in the space group P21/m of the monoclinic system, with lattice parameters of: a = 6.697(1), b = 25.483(5), c = 16.918(3)A ˚ , b = 100.03(3)_ and Z = 2. The crystals of [ZrPc2]IBr2 are built up from one-electron oxidized [ZrPc2]+ units that form stacks parallel to a axis of the crystal and mixed electron-rich trihalide ions of IBr2 _. The iodine atom of the IBr2 ions is located at the inversion center, so the IBr2 _ ions are linear and symmetrical. The mutual arrangement of [ZrPc2]+ and IBr2 _ ions is different to that found in the one-electron oxidized [ZrPc2]I3 Æ I2 complex as well as to that found in the tetragonal crystals of partially oxidized [ZrPc2](I3)2/3. EPR experiment shows that the oxidation of the diamagnetic ZrPc2 complex by IBr is ligand centered. The UV–Vis spectrum of [ZrPc2]IBr2 shows, besides the bands observed in the spectrum of ZrPc2, one additional band at _496 nm, which indicates the existence of the one-electron oxidized phthalocyaninato(1_)p-radical ligand and it is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data shows anisotropy and non-metallic character in conductivity (dr/dT > 0). The charge transport mainly proceeds along the stacks of one-electron oxidized [ZrPc2]+ units. The relatively high conductivity along the [ZrPc2]+ stack results from the staggered configuration of the Pc-rings (rotation angle 45.0(3)_) that makes short inter-ring Ca(pyrrole)–Ca(pyrrole) contacts (2.858(2)–3.017(3)A ˚ ) and greatest overlap of the HOMO orbitals that form the conduction band of the molecular materials. |
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Janczak, JanPerpétuo, Genivaldo Julio2015-02-25T16:10:38Z2015-02-25T16:10:38Z2006JANCZAK, J.; PERPÉTUO, G. J. Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. Polyhedron, v. 25, p. 3319-3329, 2006. Disponível em: <http://www.sciencedirect.com/science/article/pii/S027753870600324X>. Acesso em: 20 fev. 2015.0277-5387http://www.repositorio.ufop.br/handle/123456789/4489https://doi.org/10.1016/j.poly.2006.06.020Crystals of the new one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2 (Pc = C32H16N8) were grown directly from phthalonitrile and pure zirconium powder under the oxidation conditions of IBr at 220 _C. [ZrPc2]IBr2 crystallises in the space group P21/m of the monoclinic system, with lattice parameters of: a = 6.697(1), b = 25.483(5), c = 16.918(3)A ˚ , b = 100.03(3)_ and Z = 2. The crystals of [ZrPc2]IBr2 are built up from one-electron oxidized [ZrPc2]+ units that form stacks parallel to a axis of the crystal and mixed electron-rich trihalide ions of IBr2 _. The iodine atom of the IBr2 ions is located at the inversion center, so the IBr2 _ ions are linear and symmetrical. The mutual arrangement of [ZrPc2]+ and IBr2 _ ions is different to that found in the one-electron oxidized [ZrPc2]I3 Æ I2 complex as well as to that found in the tetragonal crystals of partially oxidized [ZrPc2](I3)2/3. EPR experiment shows that the oxidation of the diamagnetic ZrPc2 complex by IBr is ligand centered. The UV–Vis spectrum of [ZrPc2]IBr2 shows, besides the bands observed in the spectrum of ZrPc2, one additional band at _496 nm, which indicates the existence of the one-electron oxidized phthalocyaninato(1_)p-radical ligand and it is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data shows anisotropy and non-metallic character in conductivity (dr/dT > 0). The charge transport mainly proceeds along the stacks of one-electron oxidized [ZrPc2]+ units. The relatively high conductivity along the [ZrPc2]+ stack results from the staggered configuration of the Pc-rings (rotation angle 45.0(3)_) that makes short inter-ring Ca(pyrrole)–Ca(pyrrole) contacts (2.858(2)–3.017(3)A ˚ ) and greatest overlap of the HOMO orbitals that form the conduction band of the molecular materials.Zirconium diphthalocyaninePartially oxidized diphthalocyanineCrystal structureMagnetic propertiesElectrical conductivitySynthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2.info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleO periódico Polyhedron concede permissão para depósito do artigo no Repositório Institucional da UFOP. Número da licença: 3566050522747.info:eu-repo/semantics/openAccessengreponame:Repositório Institucional da UFOPinstname:Universidade Federal de Ouro Preto (UFOP)instacron:UFOPLICENSElicense.txtlicense.txttext/plain; charset=utf-82636http://www.repositorio.ufop.br/bitstream/123456789/4489/2/license.txtc2ffdd99e58acf69202dff00d361f23aMD52ORIGINALARTIGO_SynthesisCrystalCharge.pdfARTIGO_SynthesisCrystalCharge.pdfapplication/pdf564486http://www.repositorio.ufop.br/bitstream/123456789/4489/1/ARTIGO_SynthesisCrystalCharge.pdffcf26e6145ac93b2ecc07f4e0b52d18aMD51123456789/44892019-06-24 08:45:22.712oai:localhost: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Repositório InstitucionalPUBhttp://www.repositorio.ufop.br/oai/requestrepositorio@ufop.edu.bropendoar:32332019-06-24T12:45:22Repositório Institucional da UFOP - Universidade Federal de Ouro Preto (UFOP)false |
dc.title.pt_BR.fl_str_mv |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
title |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
spellingShingle |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. Janczak, Jan Zirconium diphthalocyanine Partially oxidized diphthalocyanine Crystal structure Magnetic properties Electrical conductivity |
title_short |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
title_full |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
title_fullStr |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
title_full_unstemmed |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
title_sort |
Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. |
author |
Janczak, Jan |
author_facet |
Janczak, Jan Perpétuo, Genivaldo Julio |
author_role |
author |
author2 |
Perpétuo, Genivaldo Julio |
author2_role |
author |
dc.contributor.author.fl_str_mv |
Janczak, Jan Perpétuo, Genivaldo Julio |
dc.subject.por.fl_str_mv |
Zirconium diphthalocyanine Partially oxidized diphthalocyanine Crystal structure Magnetic properties Electrical conductivity |
topic |
Zirconium diphthalocyanine Partially oxidized diphthalocyanine Crystal structure Magnetic properties Electrical conductivity |
description |
Crystals of the new one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2 (Pc = C32H16N8) were grown directly from phthalonitrile and pure zirconium powder under the oxidation conditions of IBr at 220 _C. [ZrPc2]IBr2 crystallises in the space group P21/m of the monoclinic system, with lattice parameters of: a = 6.697(1), b = 25.483(5), c = 16.918(3)A ˚ , b = 100.03(3)_ and Z = 2. The crystals of [ZrPc2]IBr2 are built up from one-electron oxidized [ZrPc2]+ units that form stacks parallel to a axis of the crystal and mixed electron-rich trihalide ions of IBr2 _. The iodine atom of the IBr2 ions is located at the inversion center, so the IBr2 _ ions are linear and symmetrical. The mutual arrangement of [ZrPc2]+ and IBr2 _ ions is different to that found in the one-electron oxidized [ZrPc2]I3 Æ I2 complex as well as to that found in the tetragonal crystals of partially oxidized [ZrPc2](I3)2/3. EPR experiment shows that the oxidation of the diamagnetic ZrPc2 complex by IBr is ligand centered. The UV–Vis spectrum of [ZrPc2]IBr2 shows, besides the bands observed in the spectrum of ZrPc2, one additional band at _496 nm, which indicates the existence of the one-electron oxidized phthalocyaninato(1_)p-radical ligand and it is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data shows anisotropy and non-metallic character in conductivity (dr/dT > 0). The charge transport mainly proceeds along the stacks of one-electron oxidized [ZrPc2]+ units. The relatively high conductivity along the [ZrPc2]+ stack results from the staggered configuration of the Pc-rings (rotation angle 45.0(3)_) that makes short inter-ring Ca(pyrrole)–Ca(pyrrole) contacts (2.858(2)–3.017(3)A ˚ ) and greatest overlap of the HOMO orbitals that form the conduction band of the molecular materials. |
publishDate |
2006 |
dc.date.issued.fl_str_mv |
2006 |
dc.date.accessioned.fl_str_mv |
2015-02-25T16:10:38Z |
dc.date.available.fl_str_mv |
2015-02-25T16:10:38Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
JANCZAK, J.; PERPÉTUO, G. J. Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. Polyhedron, v. 25, p. 3319-3329, 2006. Disponível em: <http://www.sciencedirect.com/science/article/pii/S027753870600324X>. Acesso em: 20 fev. 2015. |
dc.identifier.uri.fl_str_mv |
http://www.repositorio.ufop.br/handle/123456789/4489 |
dc.identifier.issn.none.fl_str_mv |
0277-5387 |
dc.identifier.doi.none.fl_str_mv |
https://doi.org/10.1016/j.poly.2006.06.020 |
identifier_str_mv |
JANCZAK, J.; PERPÉTUO, G. J. Synthesis, crystal structure and charge transport properties of one-electron oxidized zirconium diphthalocyanine, [ZrPc2]IBr2. Polyhedron, v. 25, p. 3319-3329, 2006. Disponível em: <http://www.sciencedirect.com/science/article/pii/S027753870600324X>. Acesso em: 20 fev. 2015. 0277-5387 |
url |
http://www.repositorio.ufop.br/handle/123456789/4489 https://doi.org/10.1016/j.poly.2006.06.020 |
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eng |
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